Cement



9 9QTING OR PLASTIC.

UNITED STATES PATENT OFFICE CEMENT Waldo E. Tyler, Kansas City, Mo., Thomas B. Douglas, Houston, Tex., Paul R. Chamberlain and Russ A. Loveland, Dewey, kla., assignors to Dewey Portland Cement Company, Kansas City, Mo., a corporation of West Virginia No Drawing. Original application January 10,

1935, Serial No. 1,154. Divided and this application September 3, 1937, Serial No. 162,296

15 Claims. (Cl. 106-25) This invention relates to a cement, the compoof a resin and an oily or fatty substance is more sition of which is such as to render it particularly satisfactory, both from the standpoint of cost satisfactory for the making of mortar for masonry and also from the standpoint of the desirability and other wall constructions and coatings. of the properties imparted to the finished product,

It has heretofore been proposed to use numerthan is the incorporation of either a resin or a ous oily, fatty and resinous substances, or comfatty substance by itself. We have further found pounds or mixtures thereof, for the purpose of that for this purpose over 0.25% by weight of increasing the plasticity or waterproofness of ceplasticizer on the dr wei ht of cement forming ment mixtures. In particular, it has been promaterials must be used. This proportion is sevposed in the Schoellkopf Patent No. 930,697 to eral times that of rosin necessary by itself to pro- 10 waterproof cement by incorporating into the cevide satisfactory grinding conditions.

ment forming material a lime salt of rosin, pre- It is therefore an object of this invention to sumably chiefly lime or calcium resinate. Other provide a composition of cement forming mateprior art patents, such as the Liebolt Patent No. rial containing a mixture of a resin and a fatty 5 847,015, disclose the use of the reaction product or oily substance in such proportions as to impart of stearin, rosin and potash for this purpose. a high degree of plasticity and workability to the l 3' 1. Further, the Lundteigen Patent No. 1,923,383 mortar into which the cement forming materials a,; discloses the use of a small quantity of a resinous may be incorporated.

material for the purpose of aiding in the grind- It is a further important object of this invening of the cement clinkers. However; the quantion to provide an improved cement of the Port- 20 tity of resinous material for this purpose is much land cement type having a high sand carrying less than that which would be necessary to imcapacity and capable of forming a mortar which part the degree of plasticity and workability dewhen hardened and dried is of relatively low sired in r product, density yet water impervious.

.- It has also been proposed in the Starke Patent It is also an object of this invention to provide 25 its No. 1,947,504 to grind cementitious material, in a masons cement of the Portland cement type which has been incorporated an inert material which maintains its plasticity for a much greater other than Portland cement and an oleaginous l gth o t e a ter a ng been worked up than material, t bt i a m t having a, v r fine the usual Portland cements, and hence does not particle size with a relatively large proportion of require remixing or retempering to maintain it in 30 particles of n i t rmediat size, proper condition for use, with consequent saving According to the present invention, a cement of in ab r a d e p and e nation of loss of extreme fineness of particle size and having dee Which Would O a y occur in remixing or sirable properties, such as its plasticity, stiffening pe i t and water t t n is bt i ed b It is a further important object of this inven- 35 cor gratin t tl ent 1ink r n tion to provide a cement of extreme fineness of grinding t erewith a suEstanhal proportion ol'a, particle size and with a plasticizer incorporated ca careous s cc, such as limestone, a small therein. w e y t C position of the cement proportion of sum and anfiyanfe an d a, very is such that it has highly desirable properties 40 minor proportion of a mixture of a're'sinous subpeculiarly adapting it for se as a masons ce- 40 stance and a fatt or oil substance. We Have merit. such as its P y, stiffening time and found that a composition of this type when made Water rete tiveness.

in accordance with our invention is peculiarly Other and further important Objects of this adapted for use as a masons cement and that it. invention will become apparent from the followpossesses properties for this purpose that are not ing descrip d ppended claims. 45 possessed by the cementitious compositions of the e Cement forming materials that are used prior t, in the preparation of a composition of our in- While incidentally the incorporation of th vention comprise various mixtures of burned armixture of resinous and oily substances, which, gillaceous and calcareous substances, and more for convenience, is referred to as a plasticizer, particularly Portland cement clinkers, with raw 50 aids in the grinding of the cementitious materials, limestone and gypsum. 0 p ster of Paris, and the main purpose in the addition of the plasticizer fl y y the term ydrite is meant a is to increase the workability and plasticity of naturally Occurring anhydrous calcium sulphate the mortar and tgincrease its stiffening time. or an artificially prepared insoluble form of an For this purpose we have found that an admixture hydrous i m sulphate. 55

In general, we prefer to employ about 50% of Portlandrce nentr linkers about 46.8% of raw limestone rocE, a small percentage, say 1.6% of gypsum, and 16% of anh drite, all expressed as 5 percentages by weighmhished mixture.

It is obvious that a lower ratio of Portland cement clinkers to limestone can be employed, or a higher ratio, but with a lower ratio there is a corresponding sacrifice in the strength of the mortar and with a higher ratio, the cost of the finished product is increased. For some purposes, however, such as where higher strength is required, the Portland cement content of our product may be run up to practically 100%.

We prefer to keep the percentage of Portland cement clinkers by weight between the rather narrow limits of 48% to 60% and vary the percentage of raw limestone rock correspondingly. The percentage of gypsum may be varied, as may also be the percentage of anhydrite, but sufiicient amounts of gypsum and anhydrite, preferably in equal proportions by weight, are incorporated into our cement to produce a product having a total 503 content between 3.0 and 3.5% by weigfitme Portland cement clinker content, and in any event above 1%. In order to obtain the desired properties in our masons cement, the incorporation of both gypsum and anhydrite is essential, although obviously either one or both may be omitted with consequent loss of the advantages that accrue from their use. The function of the anhydrite is to supply S04 ions after the S04 ions introduced as gypsum have been consumed in the formation of calcium sulpho-aluminate. The entire quantity of S04 ions required can not be introduced as gypsum because this quantity of gypsum would be sufficient to reduce the stiffening time owing to the setting of the gypsum which becomes more or less dehydrated during the process of manufacturing. The raw (unburned) limestone may be either a high grade of limestone, i. e., principally calcium carbonate, or it may contain some naturally associated clay, or silicate; or minor proportions of clay or silica may be added to the high grade limestone. The presence of a little clay adds to the plasticity of the product. Any inert equivalent calcareous substance may be substituted for the limestone, such as oyster shells, chalk, or the 5 like. Sand by itself is not an equivalent of raw limestone, although it may be added with limestone to replace a small proportion of the limestone, say up to 10 or 20% of the weight of the limestone.

The gypsum, or an equivalent retarding agent, is necessary to give the proper setting qualities to the mortar. Although other forms of calcium sulphate, such as plaster of Paris, would be satisfactory as a substitute for gypsum, plaster of Paris is, in general, too expensive to use. Gypsum is not, however, the full equivalent of anhydrite, but both must be used in order to get the best results.

The term Portland cement clinkers is here used in its accepted sense as defining a partially fused product made from argillaceous and calcareous materials by a sintering or calcining operation. It may, for instance, be made by sintering together a mixture of, say, or more of 70 limestone and the balance clay or shale. Any

suitable type of raw mix known to the art for producing Portland cement clinkers can be employed.

In making up our plasticizer, we prefer to mix 76 ordinary wood rosin, as the resinous substance,

with yellow hog fat grease as the fatty or oily component. While other types of rosin, such as gum rosin, or other resin capable of forming insoluble lime salts may be employed, wood rosin is preferable both because of its cheapness and 5 its availability. The usual grades of crude wood rosin, such as grade B resin or grade F rosin, are satisfactory for my purposes.

Similarly, other types of grease or fatty substances may be used, as for instance lard or other 10 refined hog fat, but the use of the more refined fats is objectionably expensive. Yellow hog fat grease can not be successfully used by itself in quantities necessary to give the desired results, because it makes the material being handled 15 adhere to the spouts, bins, walls, and feeders. Yellow hog fat grease contains a large percentage of oleic acid and oleates, the combined percentage of oleic acid and the glycerides of oleic acid in yellow hog fat grease being approximately 0 50% of the total weight of the grease.

The effect of varying the percentage of yellow hog fat grease and rosin in a mixture of the two upon the plasticity of the final product has been fully studied and it has been determined that, 5 starting with a 100% of rosin as the plasticizer, the plasticity of the final cement increases very rapidly with the addition of yellow hog fat grease to the rosin, until a mixture of approximately 60% rosin and 40% yellow hog fat grease is 3 reached, after which no further increase in plasticity is realized by increasing the proportion of yellow hog fat grease. For all practical purposes, the addition of 5% of yellow hog fat grease to rosin, thus forming a mixture of rosin an 35 5% of yellow hog fat grease, is entirTeTy' sa'tisfactory. The plasticity obtained by using a mixture of 95% rosin and 5% yellow hog fat grease is almost twice as good as that using rosin alone and about 20% better than that obtained by the 40 use of yellow hog fat grease alone.

Thus, although it is possible to secure some advantages by the use of either rosin alone or yellow hog fat grease alone, an unexpected advantage is secured by the use of a mixture of 45 these two ingredients in proportions of between 5 and 80% by weight of yellow hog fat grease, with the rosin making up the balance, and a mixture, specifically, of rosin and 5% yellow hog fat grease is most economical and satisfactory for our purposes. The two ingredients should be mixed together at a temperature sufficiently high so that all of the ingredients will be melted and an intimate mixture obtained. A temperature of between 250 and 300 F., preferably 250 F., will ordinarily be sufiicient to accomplish this.

It has been found necessary, in order to impart the requisite degree of plasticity and workability to the mortar into which the masons 0 cement is to be made, to incorporate over 0.3% of the mixture of rosin and yellow hog fat grease by welg o t e dry mix ure 0 cemen ormin materials. Expresse 1 eren y, we n a in order to secure the results desired, it is impracti- 5 cal to use less than one pound of the rosin-fat mixture to a barrel of the finished cement forming materials, weighing 268 pounds. This figures out to be about 0.37% of the rosin-fat mixture by weight of the total cement mixture. While 7 it is possible to increase the amount of the rosinfat mixture to a percentage above 3%, further additions of the mixture beyond that percentage do not result in any appreciable added plasticity or workability and tend to lessen the strength 75 of the mortar, as well as to increase the cost of making the same.

The incorporation of the plasticizer into the cement forming materials is preferably carried out diu'ing the grinding of the Portland cement clinkers. In a triple stage grinding operation, using a roller type and two tube mills, the plasticizer is added to the gypsum and the mixture introduced into the stream of clinkers, which may be still warm, but not sufliciently hot to decompose the plasticizer. The addition of the plasticizer may be made either prior to grinding in the first mill or subsequent thereto. The anhydrite may be added at the same time, or the rosin-fat mixture may be incorporated into a mixture of the gypsum and anhydrite. Preferably, a mixture of gypsum and plasticizer is introduced into the stream of clinkers at the same time that the raw limestone is, and the resulting mixture conveyed into the first mill and thence into the second and third mills.

Preferably, no free lime as such is present in my cement, although upon use of the cement with water approximately 7% of calcium oxide is liberated.

The grinding operation, which is carried out at a temperature of about 250 F., serves to comp e e y an oroug y mix e rosin, hog fat grease and other ingredients. As previously stated, the proportions of gypsum, anhydrite and limestone rock may be varied through a considerable range, but best results have been obtained by varying the proportions of gypsum and anhydrite through a narrow range only, and in accordance with the percentage of sulphur trioxide (S03) in the gypsiun and anhydrite so as to maintain the total percent of sulphur trioxide radical (S03) at between 3.0 and 3.5% by weight of the Portland cement clinker content (dry). If sulficient gypsum alone were added to obtain the relatively high S03 content of our cement, the mortar made therefrom would set too quickly. The use of a relatively insoluble anhydrous calcium sulphate, such as anhydrite, permits the use of a relatively high percentage of S03 to obtain the accompanying increase in strength without sacrifice of the stiffening time. Anhydrite is sumciently soluble in the mortar mix to furnish, with the gypsum, enough Ca and S04 ions to form with the alumina compounds contained in the clinker a calcium sulpho-aluminate.

The cementitious mixture is ground in the mills to a fineness preferably such that about 98% by weight of the mixture passes through a 325 mesh screen. A typical sample of our masons cement shows the following degree of fineness, expressed in terms of the mesh through which the product will pass and also in terms of diameters of particles expressed in microns, as determined by means of a Wagner turbidimeter:

Percent by weight The calculated surface area of a typical masons cement of our invention is 3520. Under similar conditions of grinding, it was found that the use of straight rosin gave a surface area of 3620 and of yellow hog fat grease alone gave a surface area of 3290.

The degree of fineness indicated by the foregoing table is very much finer than that of ordinary standard Portland cement. The table indicates that more than 50% by weight of the masons cement of our invention will be made up of particles having a size less than 7.5 microns and less than 1% of particles having a size greater than 35 microns.

The resulting composition of our masons cement can be used in the usual way for making up into a mortar, for use by bricklayers, plasterers and similar artisans. For this purpose, the cement is mixed with sand and water incorporated into the mass until the proper consistency has been obtained. The proportions of sand and water can be greater than those customary in the art using previously known masons cements. As much as 4 to 7 parts by weight of sand to 1 part of our masons cement can be used with satisfactory results, owing to the high degree of plasticity of our product. Previously, 4 to 1 was about highest average ratio of sand to cement by weight that was practical.

We attribute the improved sand carrying capacity of our cement to the usepf our.pla sticizer. Observat ons show that when our cement is mixed into a mortar with sand and water, minute air bubbles are formed in immense numbers and that 'tfiese air"bubbles persist during the mixing and subsequent hardening of the mortar. When our plasticizer is omitted or used in percentages below about 0.3% by weight of the mixture, or when rosin or fat alone is used, there is no such extensive formation of air bubbles in the mortar mix and its sand and water carrying capacity is greatly reduced.

Because of the air bubble formation, mortar prepared from our cement has a much lower density after hardening and drying than previously known straight Portland cement mortars. For example, mortar using our cement, hardens and dries to give a mass having a density of from 105 to 115 lbs. per cu. it. as compared with over 130 lbs. per. cu. ft. for straight Portland cement mortars or concretes.

The mortar so formed from the masons cement of our invention has greatly improved properties of plasticity and is easily and smoothly workable with the trowel. In using the mortar of this invention for the laying of bricks, we have found that the mortar strings well. By this is meant that the mortar may be strung out from the masons trowel over a course of bricks as far as the mason can conveniently reach without breaking the continuity of the layer or string of mortar. The mortar does not set up too rapidly for convenient handling but works well. These properties are very important in a bricklayers mortar and have not, to the best of our knowledge, been previously obtained in a mortar prepared from Portland cement materials.

The term plasticity, as herein used, includes a number of properties variously referred to as water rententiveness, butteriness, fattiness, etc., and combines the qualities of water retentiveness, paste per unit volume, stiffening time, lubricating qualities and other qualities of like nature. A measure of plasticity is a measure of the desirability of the mortar from the masons standpoint.

The ideal stiffening time would be several hours, that is, long enough so that the mortar could be mixed rapidly in large quantities and be permitted to stand during the day while being used as required. If the stifiening time were too long, however, it would lap over the period when the mortar should have obtained an appreciable strength, and this in some cases would not be desired.

The plasticity should be high enough so that the mason can handle the mortar with the maximum quantity of sand and still obtain a strong, water tight mortar. The plasticity of a masons cement using as plasticizer rosin by itself is not high enough to do this, whereas if a mixture of rosin and yellow hog fat grease within the proportions above indicated is used, the plasticity of the resulting mortar is high enough for this purpose.

A test on a plasticimeter of mortar prepared from our masons cement using one part of mason's cement to 4 parts of standard Ottawa sand by weight gives the following results, depending upon the composition of the plasticizer:

Plasticizer Index number Rosin alone Yellow hog fat grease alone 105 95% rosin and 5% yellow hog fat grease 124 Plasticizer stiffening time Rosin alone 11 min. Yellow hog fat grease alone 22 min.

95% rosin and 5% yellow hog fat grease 22 min.

From the foregoing table it is apparent that the use of a mixture of rosin and yellow hog fat grease, such as a mixture containing 95% rosin and 5% yellow hog fat grease, gives a greatly increased plasticity over the use of either rosin alone or yellow hog fat grease alone and gives a similar stifiening time to that obtained by using yellow hog fat grease alone, but a considerably longer stiiTening time than that obtained by using rosin alone. As previously stated. the percentage of yellow hog fat grease in the plasticizer may be increased materially, but the mixture of 95% rosin and 5% yellow hog fat grease costs materially less than a plasticizer made with, say 40% rosin and 60% yellow hog fat grease.

In addition to the foregoing properties, our cement has a surprisingly high early and 28 days strength considering its high limestone content. Its 1 day strength approaches that of a 100% Portland cement mix, although our cement has only a 50% Portland cement content.

This application is a division of our application Serial No. 1,154, filed January 10, 1935.

We are aware that numerous details of the process may be varied through a wide range without departing from the principles of this invention, and we, therefore, do not purpose limititing the patent granted hereon otherwise than necessitated by the prior art.

We claim as our invention:

1. A composition of cementitious materials, comprising a mixture of burned argillaceous and calcareous substances, an inert unburned calcareous substance, gypsum, anhydrite and over 0.3% of a plasticizer by weight of said mixture, said plasticizer comprising a mixture of rosin and a fat.

2. A composition of cementitious materials, comprising a mixture of burned argillaceous and calcareous substances, an inert unburned calcareous substance, calcium sulphate and over 0.3% of a plasticizer by weight of said mixture, said plasticizer comprising a mixture of rosin and yellow hog fat grease.

3. A composition of cementitious materials suitable for use in making a bricklayers mortar, comprising a mixture of burned argillaceous and calcareous substances, an inert unburned calcareous substance, gypsum, anhydrite and over 0.3% of a plasticizer by weight of said mixture, said plasticizer comprising a mixture of rosin and yellow hog fat grease in the proportion of from 95 to 20% rosin and 5 to yellow hog fat grease.

4. A masons cement comprising a finely ground mixture containing less than 1% by weight of particles exceeding 35 microns in diameter and more than 50% of particles less than 7.5 microns in diameter, the mixture containing Portland cement clinkers, raw limestone, gypsum, anhydrite and a mixture of a rosin and a fat as a plasticizer.

5. A masons cement comprising a finely ground mixture containing less than 1% by weight of particles exceeding 35 microns in diameter and more than 50% of particles less than 7.5 microns in diameter, the mixture containing Portland cement clinkers, raw limestone, gypsum, anhydrite and over 0.3% by weight of said mixture of a mixture of a rosin and a fat as a plasticizer.

6. A masons cement comprising a finely ground mixture containing less than 1% by weight of particles exceeding 35 microns in diameter and more than 50% of particles less than 7.5 microns in diameter, said mixture comprising Portland cement clinkers, raw limestone, gypsum, anhydrite and over 0.3% by weight of said mixture of a plasticizer consisting of to 20% of rosin and 5 to 80% of a fat by weight.

7. A masons cement comprising a finely ground mixture containing less than 1% by weight of particles exceeding 35 microns in diameter and more than 50% of particles less than 7.5 microns in diameter, said mixture comprising Portland cement clinkers, raw limestone, gypsum, anhydrite and over 0.3% by weight of said mixture of a plasticizer consisting of 95% rosin and 5% yellow hog fat grease.

8. A masons cement comprising a finely ground mixture containing less than 1 by weight of particles exceeding 35 microns in diameter and more than 50% of particles less than 7.5 microns in diameter, sa d mixture comprising Portland cement clinkers. raw limestone, an amount of calcium sulphate suificient to give an S03 content by weight of the Portland cement olinkers equal to 3.0 to 3.5% and over 0.3% by weight of said mixture of a plasticizer consisting of 95 to 20% of rosin and 5 to 80% of a fat by weight.

9. A masons cement having the substantially following composition, expressed in per cent by weight:

Per cent Portland cement clinker 50. Unburned limestone 46.8 Gypsum 1.6 Anhydrite 1.6 Plasticizer 0.37 to 3% of mixture Rosin 95 Fat 5 10. A cement comprising a mixture of cementitious materials including a major proportion of Portland cement clinkers and from 0.3 to 3.0% of I06. COMPOSITIONS,

COATING OR PLASTIC.

a plasticizer comprising rosin and a fat, said mixture being finely ground together to contain less than 1% by weight of particles exceeding 35 microns in diameter and more than 50% of particles less than 7.5 microns in diameter.

11. A cement comprising a mixture of cementitious materials including a major proportion of Portland cement clinkers, a substantial proportion of raw limestone, a proportion of gypsum and anhydrite sufficient to give an $03 content of between 3.0 and 3.5% on the weight of the Portland cement clinkers in the finished cement and from 0.3 to 3.0% of a plasticizer comprising rosin and a fat, said mixture being finely ground together to contain less than 1% by weight of particles exceeding 35 microns in diameter and more than 50% of particles less than 7.5 microns in diameter,

12. The method of making a cement, which comprises preparing an intimate mixture having a major proportion of Portland cement clinkers and containing between 0.3 and 3.0% of a mixed resin and a fat, and grinding said mixture until the ground product contains less than 1% of particles exceeding 35 microns in diameter and more than 50% of particles of less than 7.5 microns in diameter.

13. The method of making a cement, which comprises introducing into a mixture having a major proportion of Portland cement clinkers, a substantial proportion of raw limestone, minor proportions of gypsum and anhydrite, between 0.3 and 3.0% by weight of the mixture of a mixed resin and a fat, and grinding said mixture until the ground product contains less than 1% of particles exceeding 35 microns in diameter and more than 50% of particles of less than 7.5 microns in diameter.

14. The method of making a masons cement, which comprises introducing into a mixture of approximately equal proportions of Portland cement clinkers and raw limestone, and containing gypsum and anhydrite, between 0.3 and 3.0% by weight of a mixed resin and a fat, and grinding said mixture until the ground product contains less than 1% of particles exceeding 35 microns in diameter and more than 50% of particles of less than 7.5 microns in diameter.

15. The method of making a masons cement, which comprises preparing an intimate mixture of Portland cement clinkers, raw limestone, gypsum and anhydrite containing between 0.3 and 3.0% by weight of the mixture of a mixed resin and a fat, and grinding said mixture until the ground product contains less than 1% of particles exceed ing 35 microns in diameter and more than 50% of particles of less than 7.5 microns in diameter.

WALDO E. TYLER. THOMAS B. DOUGLAS. PAUL R. CHAMBERLAIN. RUSS A. LOVELAND. 

